Benzene phosphonous acid compounds, their production and use as stabilizers for organic materials

ABSTRACT

The purpose of the invention are new benzene phosphonous acid compounds in which two to four benzene nuclei are bound together and which contain one to three phosphorus atoms. The new compounds are free acids, their salts with inorganic cations, their esters, thioesters or amides. The invention concerns also the manufacture of these benzene phosphonous acid compounds and their use for the stabilization of organic materials.

This application is a division of our copending application Ser. No.191,079 filed Oct. 20, 1971 and now U.S. Pat. 3,825,629.

The purpose of the invention are new benzene phosphonous acid compoundsin which two to four benzene nuclei are bound together and which containone to three phosphorus atoms. The new compounds are free acids, theirsalts with inorganic cations, their esters, thioesters or amides. Theinvention concerns also the manufacture of these benzene phoshonous acidcompounds and their use for the stabilization of organic materials.

The invention relates to a process for the production of new benzenephosphonous acid compounds of formula ##SPC1##

Wherein m means 1 or 2, A unsubstituted or substituted diphenyl orterphenyl,

Q the single bond or an unsubstituted or substituted phenylene radical,X₁ a radical of formula ##EQU1## and X₂ hydrogen or a radical of formula##EQU2## R₁, R₂, R₃ and R₄ independent of each other stand for hydrogenor an unsubstituted or a substituted hydrocarbon radical, containing upto 16 carbon atoms,

Y for oxygen, sulfur or the radical of formula ##EQU3## and Z, eitherbound to R, together with the N-atom, for a heterocyclic ring or for R₁,R₂, R₃ or R₄, which process is characterized by the reaction of 1 mol ofa compound of formula ##SPC2## WHEREIN Hal means halogen and X₃ hydrogenor a radical of formula

    -- P (Hal).sub.2                                           (V)

with so many mols of a compound of formula

    R.sub.1 -- Y -- H                                          (VI)

or of a mixture of 2, 3 or 4 compounds of formulae R₁ -- Y -- H, R₂ -- Y-- H, R₃ -- Y-- H and R₄ -- Y -- H, as Hal-radicals are present in thecompound of formula (IV).

The starting materials of formula (IV) used in the present invention arenew. They are produced from unsubstituted or substituted aromatichydrocarbons, which are composed of 2, 3 or 4 benzene nuclei, boundtogether by a single bond. Examples for such hydrocarbons are: Diphenyl,o-, m- and p- terphenyl, m- quaterphenyl, p- quaterphenyl,1,2,4,-triphenyl-benzene and 1,3,5-triphenyl-benzene. From thesestarting materials the compounds of formula (IV) are produced by rectionwith a phosphorus trihalide, preferably with phosphorus trichloride.This reaction can be performed at very high temperatures in the gaseousphase. To avoid side-reactions it is, generally, advantageous to workunder milder conditions, using catalysts. Friedel-Crafts-Catalysts aresuitable, especially anhydrous aluminium chloride. One preferably workswith a surplus of phosphorus trichloride at its boiling temperature.Working up the reaction mixture, the aluminium chloride complex with thedichlorophosphil is first decomposed, for instance with phosphorusoxychloride or with pyridine. Principally these methods of manufactureare known. These and other analogous procedures for the production ofcompounds of formula (IV) are collectively described by K. Sasse in"Handbuch von Houben-Weyl, Methoden der organischen Chemie, 4th Edition(1963), Vol. XII/1, organische Phosphorverbindungen", part 1, pg.302-318.

The starting matrials, characterized by formula (VI), are: Water,hydrogen, sulfide, ammonia, alcohols, phenols, mercaptans, thiophenolsand organic primary and secondary amines.

The reaction of the starting materials of formula (IV) and (VI) normallyproceeds easily; to avoid side-reactions, it is often necessary tosmooth the vehement reaction by cooling externally. Reacting with water,it is preferred to use it in surplus, to cool and to add thehalophosphine of formula (IV) so slowly, that the temperature does notrise too high by the exothermic reaction. Accomplishing the hydrolysisin this way, there result colorless, powdery compounds, containingradicals of the following structure: ##SPC3##

These derivatives of the benzene phosphonous acid have acid propertiesand, by treating with inorganic bases or with salts containing inorganiccations, are transferred in their corresponding salts. Examples for suchinorganic reagents are: Calcium hydroxide, zinc-oxide, sodium carbonate,potassium hydrogen carbonate, aluminium acetate, barium chloride, nickelacetate and zinc chloride. The hydrolysis of halophosphines of formula(IV) and the transformation of the hydrolysis products, which containradicals of the above formulae (VIIa) or (VIIb) into their salts, mayalso be performed in a one step process. For this purpose, as describedabove, the water used for the hydrolysis is put in surplus in advance,together with the desired inorganic reagent, followed by thehalophosphine of formula (IV), which is slowly added by stirring.Humidity is carefully excluded if, instead of water, other compounds offormula (VI) are to be reacted. Generally phenols react smoothly ifheated for instance to 100-150°C, whereby the hydrogen halide splitsoff.

Acid binding agents, such as pyridine or trialkylamines can be added tobind the split off hydrogen halide.

This method is preferred if alcohols are reacted. If the compounds offormula (IV) are reacted with organic amines or with ammonia, these areused in a surplus, which serves as a binding agent for the hydrogenhalide split off.

The described reactions are analogous processes, which are generallyknown. A respective collective summary has been published in theafore-mentioned book by K. Sasse (compare p. 318 ff.). Substituents inthe polyphenyl compounds, characterized by the symbol A [formulae (I)and (IV)] and Z[formula (III) ] are alkyl- and cycloalkyl groups.Examples for such substituents are: Methyl, ethyl, propyl, butyl,isobutyl, amyl, 2,2-dimethylpropyl, octyl, dodecyl, isopropyl,tert.-butyl, 2,6,8-trimethyl-4-nonyl, 2-ethyl-hexyl,2,4,6,8-tetramethylnonyl, cyclododecyl.

The preferred polyphenyl compounds and the phenylene radical Q areunsubstituted; they may be substituted by halogen, especially bychlorine and bromine or by alkoxy radicals such as methoxy, ethoxy,propoxy, isopropoxy, butoxy, hexyloxy, dodecyloxy and 2-ethylhexyloxy.

Besides the abovementioned hydrocarbon radicals which can stand for Rand Z, the latter can also mean aryl radicals, which as well as thealkyl radicals, may be substituted. Examples are the followingsubstitutents: Phenyl, 2-, 3- or 4-methylphenyl, dimethylpheyl (mixtureof isomers), p-tert.butylphenyl, 2-methoxyphenyl, 3-chlorophenyl anddichlorophenyl (mixture of isomers), 2-methoxyethyl, 2-methoxypropyl,2-phenoxyethyl, 2-(2'-phenoxyethoxy)-ethoxy, 2-cresoxyethyl, benzyl,4-chlorobenzyl, 2,4-dichlorobenzyl, 2-chloroethyl and substituents offormula

    CH.sub.3 (OCH.sub.2 CH.sub.2).sub.p --                     (VIII)

wherein p means one of the numbers 2 to 12.

Examples for those cases, in which the radicals Z and R are connectedwith each other and form, together with the N-atom [formula (III)] aheterocyclic ring, are the heterocyclic substituents pyrrolidino,piperidino, hexamethylenimino and morpholino. The invention alsoconcerns the new compounds of formula (I) and their use as stabilizers,particularly such use of compounds of the formula ##SPC4##

wherein Y is oxygen or sulphur and

n is 1 or 2.

For this purpose the new compounds are either incorporated in theproduct or material sensitive to light, oxygen and heat, or applied toits surface to form a protective film. By their stabilizing effect theyprotect these sensitive substances from degradation. They have a widerange of application in the processing of plastics; to name someexamples, they can be employed as stabilizers for cellulose acetate,cellulose proprionate, cellulose acetobutyrate, polyethylene,polypropylene, polyvinyl chloride, polyvinyl chloride-actate,polyamides, polystyrene, ethyl cellulose, cellulose nitrate, polyvinylalcohol, silicon rubber, melamineformaldehyde and urea-formaldehyderesins, allyl cast resins, polymethylmethacrylate, polyesters andpolyacrylonitrile. The compounds can also be used to protect naturalproducts such as rubber, cellulose, wool and silk from degradation. Theproducts or materials for protection may be present in the form of sheetor film, panels, tubing, rods, tapes, coatings, fibres, granules,powders or other solid forms, or as solutions, emulsions or dispersions.The stabilizers are incorporated in, or applied to these materials bythe known methods. One of the main methods of application is intimatemixing of the stabilizer and the plastic material, e.g. polypropylenegranules, in a kneading or other suitable machine and extrusion mouldingof the mixture. This technique ensures homogeneous blending, which isimportant for effective protection. Extrusion moulding is employed toproduce a variety of products, including films, tubing and filaments.The latter can be converted into woven fabrics.

If polypropylene, for instance, is to be processed as woven fabric thestabilizer is normally mixed with it prior to extrusion as filamentyarn. However, these new stabilizers can be applied with equally goodeffect to textile yarns and fabrics, for example from an aqueous bathcontaining the compound of formula (I) in superfine dispersion. Textilesof polyester and cellulose acetate fibres are suitable for this exhaustmethod of application. The plastics need not necessarily be polymerizedwhen the new compounds are added. The latter can be blended with themonomers or prepolymers prior to the condensation or otherpolymerization reaction yielding the final polymer.

Besides their use for the stabilization of clear films, plastics and thelike, the new stabilizers are suitable for application in or on opaque,semi-opaque and translucent materials having a surface which is subjectto degradation by light, oxygen and heat. Examples of such materials arefoamed plastics, opaque film and sheeting, opaque papers, transparentand opaque pigmented plastics, fluorescent pigments and automobile andfurniture polishes, creams, lotions and similar products, which lattergroup of products may be opaque, clear or translucent.

Benzene phosphonous acid esters and their stabilizing effect are knownfrom literature. Comparing these compounds, for instance with thosedescribed in the Belgian patent 724 802, the new compounds of formula(I) have essential advantages. They are less fugitive, have lessinclination for migration and are better soluble in many materials to beprotected. Moreover the connection of at least two benzene nuclei in thenew compounds of formula (I) has the effect, they they absorb ultraviolet rays. They therefore do not only protect against heat and oxygenbut also against the decomposition of sunlight. Any comparablephosphorus compunds have none such combined protective effect. In spiteof this polyvalent effect it is in many cases advantageous to mix thenew stabilizers with other types of light absorbers or of stabilizers.

Those mixtures of agents have often a synergistic effect and protect thetreated materials at the same time in a particularly high degree againstultra violet light, heat and oxydative desintegration.

As explained above the new compounds of formula (I) can be used asstabilizers for various organic materials. Depending the kind and numberof the substituents the compounds of formula (I) are more or less suitedfor the protection of a certain organic material. The followingrelations between the chemical constitution of the compounds of formula(I) and plastics, which have to be protected, have for instance beenobserved: To protect polypropylene, such agents are especially suited,which contain one or several aliphatic or cycloaliphatic radicals whichcontain at least 6, preferably 8 to 20 carbon atoms. To protectpolyvinylchloride such agents are especially suited, whose substitutentsR contain aryl radicals, which may be substituted with lower alkylradicals or with chloro atoms. For the protection of polyesters and ofpolyamides those agents are especially suited which contain severalether groups in the substituents R. The present invention concerns alsothe materials which contain compounds of formula (I) for stabilization.As shown above in some examples, the incorporation of the new compoundsinto the materials that need protection can be effected at any stage ofprocessing according to known methods, whereby the amount of addedprotective agents may vary within wide limits, for instance between 0.01and 5 %, preferably between 0.05 to 1 %, related to the materials thatneed protection.

In the following examples F means melting point; Kp boiling point; λwavelength, λmax the wavelength of maximum light absorption in nanometerunits; parts and per cents are by weight and temperatures in degreescentigrades.

EXAMPLES FOR THE PRODUCTION OF THE INTERMEDIATE PRODUCTS OF FORMULA (IV)

a. In the absence of moisture a solution of 46.2 parts of diphenyl, 165parts of phosphorus trichloride, and 44.8 parts of AlCl₃ is heated underreflux during the course of 3 hours; 53.5 parts of phosphorusoxychloride are subsequently added and the mixture is stirred for afurther 15 minutes. After cooling to 0° the AlCl₃ POCl₃ complex,precipitated in the form of granules, is filtered off, is washedthoroughly with chlorobenzene, and the filtrate is evaporated in avacuum. As residue 65 parts (85% of theory) of4-diphenyl-dichlorophosphine of formula ##SPC5##

are obtained in the form of a red, light oil of a pungent smell.

b. Working up is effected as described under a), but in place of 44.8parts of AlCl₃, 106 parts are used, and in place of 53.5 parts ofphosphorus oxychloride, 122.6 parts are used. Thus, 85.2 parts of4,4'-diphenyl-bis-(dichlorophosphine) of formula ##SPC6##

are obtained in the form of a red, light oil of a pungent smell.

c. In the absence of moisture a solution of 34.5 parts of p-terphenyl,330 parts of phosphorus trichloride, and 52 parts of aluminium chlorideare heated under reflux during the course of 5 hours; 61.3 parts ofphosphorus oxychloride are subsequently added and the mixture is stirredfor a further 15 minutes, is cooled to 0°, the resulting Al-complex isfilered off, is washed with phosphorus trichloride, and the filtrate isevaporated in a vacuum.

As residue 29 parts of 4,4"-(p-terphenyl)-bis-(dichlorophosphine) offormula ##SPC7##

are obtained in the form of light yellow crystals.

EXAMPLES FOR THE END-PRODUCTS OF FORMULA (I)

are listed in the following table 1 where the melting points ofcrystalline compounds are indicated in column F. These compounds melt ata temperature considerably higher than room temperature. The otherindicated compounds are specified in column F as `oil`.λmax. means themaximum of light absorption which is expressed by nanometer (nm) units.The constitution formulae indicated in table 1 are confirmed byelementary analyses.

                                      Table 1                                     __________________________________________________________________________    Exple                                                                             Constitution of the compounds of                                                                    F       λmax                                 No. general formula               (nm)                                               R.sub.1    R.sub.2                                                     __________________________________________________________________________     1  --O--C.sub.4 H.sub.9                                                                      R.sub.1 = R.sub.2                                                                       oil     252                                          2  --O--C.sub.8 H.sub.17 (iso)                                                               R.sub.1 = R.sub.2                                                                       oil     250                                          3  C.sub.9 H.sub.19                                                                          R.sub.1 = R.sub.2                                                                       oil     253                                          4  C.sub.9 H.sub.19                                                                          --O--C.sub.4 H.sub.9                                                                    oil     254                                          5  C.sub.9 H.sub.19                                                                          --O--C.sub.8 H.sub.17 (iso)                                                             oil     253                                          6  --S--C.sub.12 H.sub.25                                                                    R.sub.1 = R.sub.2                                                                       42-43°                                                                         270                                          7            * R.sub.1 = R.sub.2                                                                     * 110-111°                                                                       255                                          8              R.sub.1 = R.sub.2                                                                       168-169°                                                                       263                                                R.sub.1    R.sub.2                                                      9  --O--C.sub.4 H.sub.9                                                                      R.sub.1 = R.sub.2                                                                       oil     260                                         10  --O--C.sub.8 H.sub.17 (iso)                                                               R.sub.1 = R.sub.2                                                                       oil     259                                         11  --O--C.sub.13 H.sub.27                                                                    R.sub.1 = R.sub.2                                                                       oil     259                                         12            * R.sub.1 = R.sub.2                                                                     * 94-96°                                                                         273                                         13  C.sub.9 H.sub.19                                                                          R.sub.1 = R.sub.2                                                                       oil     265                                         14  C.sub.9 H.sub.19                                                                          --O--C.sub.8 H.sub.17                                                                   oil     268                                         15  --S--C.sub.12 H.sub.25                                                                    R.sub.1 = R.sub.2                                                                       54-56°                                                                         300                                         16            * R.sub.1 = R.sub.2                                                                     * 184-186°                                                                       250                                         17  --N(C.sub.4 H.sub.9).sub.2                                                                R.sub.1 =R.sub.2                                                                        oil     261                                         18  C.sub.9 H.sub.19                                                                          --O--C.sub.8 H.sub.17 (iso)                                                             oil     271                                         19   C.sub.9 H.sub.19                                                                         --O--C.sub.4 H.sub.9                                                                    oil     262                                         20            * --O--C.sub.4 H.sub.9                                                                    oil     264                                         21  --S--C.sub.12 H.sub.25                                                                    --O--C.sub.8 H.sub.17 (iso)                                                             oil     264                                             R.sub.1     R.sub.2                                                       22  --O--C.sub.8 H.sub.17                                                                     R.sub.1 = R.sub.2                                                                       oil     292                                         23            * R.sub.1 = R.sub.2                                                                     *  199-199,5°                                                                    298                                         24  C.sub.9 H.sub.19                                                                          R.sub.1 = R.sub.2                                                                       oil     292                                         25  C.sub.9 H.sub.19                                                                          --O--C.sub.4 H.sub.9                                                                    oil     292                                         26  --S--C.sub.12 H.sub.25                                                                    R.sub.1 = R.sub.2                                                                       63-65°                                                                         308                                         27            * R.sub.1 = R.sub.2                                                                     * 187-189°                                                                       310                                         28  --N(C.sub.4 H.sub.9).sub.2                                                                R.sub.1 = R.sub.2                                                                       oil     296                                         __________________________________________________________________________     * The symbols +  signify the tertiary butyl radical.                     

EXAMPLES FOR THE PRODUCTION OF END-PRODUCTS OF FORMULA (I)

The Examples are numbered in the same way as the corresponding compoundsof the above table 1.

EXAMPLE 7

In the absence of moisture a solution of 43.5 parts of4-diphenyldichlorophosphine [Example (a), formula (IX)] in 100 parts oftoluene is added at 0°-5° to 56.8 parts of 4-tert.butyl thiophenol and35 parts of triethylamine in 200 parts of toluene; the mixture isallowed to react over night at 40°, the precipitated triethyl ammoniumchloride is filtered off, the filtrate is evaporated in a vacuum, andthe oily residue is purified by crystallization from methanol-ether.Constitution formula and characterization of this compound and thecompounds of the production Examples cited below are indicated in theabove table 1.

EXAMPLE 9

In the absence of moisture a solution of 28.35 parts of4,4'-diphenyl-bis-(dichlorophosphine) [Example (b), formula (X)]in 100parts of chlorobenzene is added at 0°-5° to 23.6 parts of n-butanol and32 parts of triethylamine in 300 parts of chlorobenzene; the mixture isallowed to rect over night at 40°, the precipitated salt is filteredoff, the filtrate is evaporated in a vacuum, and a light yellow oil isobtained.

EXAMPLE 13

A solution of 47.5 parts of 4,4'-diphenyl-bis-(dichlorophosphine) in 100parts of toluene is added at 0°-5° to 117.5 parts of 4-nonylphenol and55 parts of triethylamine in 400 parts of toluene; the mixture isallowed to react overnight at 50°-60°, the precipitated triethylammonium chloride is filtered off, the filtrate is evaporated in avacuum, and thus, a yellow viscous residue is obtained.

The same compound is also obtained by mixing the starting materialswithout triethylamine and without toluene and gradual heating to140°-160°, while there is passed carbon dioxide through the mixture,until the evolution of hydrogen chloride ceases.

EXAMPLE 15

A solution of 20.0 parts of 4,4'-diphenyl-bis-(dichlorophosphine) in 100parts of toluene is added at 0°-5° to 45.4 parts of dodecyl mercaptanand 22.8 parts of triethylamine in 200 parts of toluene; the mixture isthen allowed to react overnight at 40°, the precipitated triethylammonium chloride is filtered off, the filtrate is evaporated in avacuum, and the residue is crystallized from ether.

EXAMPLE 27

A solution of 31.0 parts of 4,4"-(p-terphenyl)-bis-(dichlorophosphine),Example (c), formula (XI), is added at 0°-5° to 48.1 parts of4-tert.butyl thiophenol and 30.1 parts of triethylamine in 300 parts oftoluene; the mixture is allowed to react over night at 40°, theprecipitated triethyl ammonium chloride is filtered off, the filtrate isevaporated in a vacuum, and the residue is crystallized frombenzene-methanol.

In place of 30.1 parts of triethylamine, 24 parts of anhydrous pyridinemay also be used as acid-binding agent.

In Examples 4, 5, 14, 18, 19, 20, 21, and 25 of table 1 there arementioned esters of phosphonic acids which contain in the same moleculeradicals derived from different alcohols, phenols or mercaptans. Theproduction thereof is effected in analogous manner as described in theabove production Examples by reacting the chlorphosphines with a mixtureof the corresponding reaction partners. Thus, mixtures of esters arealways obtained; aside from the main constituents which arecharacterized by the formulae of Examples 4, 5, 14, 18, 19, 20, 21, and25 these mixtures also contain other esters, wherein the equivalentratio of the radicals is shifted.

The following Examples relate to end-products which are obtained byhydrolysis of 4,4'-diphenyl-bis-(dichlorophosphine) of formula (X),partly as free phosphonous acids, partly in the form of the salts withinorganic cations.

EXAMPLE 29

80 parts of 4,4'-diphenyl-bis-(dichlorophosphine) of formula (X),produced as described in Example (b), are diluted with 20 parts ofchlorobenzene and slowly added to 300 parts of water while stirringwell, and the temperature is kept at 0°-5° by external cooling. Thereaction is completed at 20° after 18 hours. The thin colourlessprecipitate is filtered off and is dried at 90° in a vacuum. Theobtained crude product is appropriate for the use as stabilizer. Itmainly consists of the compound of formula ##SPC8##

and impurities which probably consist of anhydrides of the acid offormula (XII). Other impurities furthermore contain chlorine, as a smallpart of the chlorine atoms in the starting product of formula (X) hasescaped from hydrolysis by coating with the insoluble precipitate.

EXAMPLE 30

The process described in Example 29 may be simplified by renouncing theisolation of the intermediate product of formula (X) as well as thepurification thereof (precipitation of the aluminum chloride byphosphorus oxychloride).

46.2 parts of diphenyl, 106 parts of aluminum chloride, and 165 parts ofphosphorus trichloride are heated under reflux during the course of 2hours; the excess of phosphorus trichloride is subsequently removed bydistillation and the viscous residue is taken up in 40 parts ofchlorobenzene. Hydrolysis is then effected with 300 parts of water asdescribed in Example 29. The obtained fine colourless powder contains16.7% of phosphorus, 1.1% of chlorine, and 3.8% of aluminium.

EXAMPLE 31

The 4-diphenyl-dichlorophosphine of formula (IX) described in Example(a) is hydrolized in accordance with methods described in Example 29;after the working up a colourless fine powder is obtained which mainlyconsists of the compound of the following formula ##SPC9##

EXAMPLE 32

26 parts of the compound obtained in accordance with Example 29 aremixed by stirring with a solution of 21 parts of barium chloride in 100parts of water and boiled under reflux during the course of 3 hours.After cooling to 5° the colourless precipitate is filtered, is washedwith water and is dried at 90° in a vacuum. The resulting barium saltcontains 18.9% of barium.

In analogous manner the light green nickel salt (content of nickel is6%) is obtained from 25 parts of nickel acetate and the colourless zincsalt (content of zinc is 4.1%) from 27 parts of chloride of zinc.

EXAMPLE 33

Proceeding in manner analogous to that described in Example 30 theresulting colourless powder is suspended in 400 parts of water whilestirring: calcium oxide is gradually added at such an amount that afterstirring at 80° for a longer period the pH value does not sink below 5°;the mixture is cooled to 5° and the precipitate is filtered. Theresulting colourless salt contains 4.1% of calcium, 6.3% of aluminum,and 3.3% of chlorine.

EXAMPLES FOR THE USE OF END-PRODUCTS OF FORMULA (I)

A. stabilization against oxidative degradation

A few of the compounds cited in the above Examples are tested in view oftheir effect as stabilizers against oxygen as follows: 0.1% of acompound of formula (I) are homogeneously incorporated in polypropylenewhich contains 0.2% of 4,4'-methylen-bis-(2,6-di-tert.butylphenol) asantioxydant agent. After displacing the air, the plastics in the form ofthin small plates is then kept under oxygen in a closed system. Then itis heated to 190°, whereby an overpressure of about 20 mm Hg takesplace. The oxidation of the plastics results in a decrease of pressure.The rate of this decrease of pressure is small if the effectiveness ofthe stabilizer or the mixture of the stabilizers is high. The testresults are summarized in the following table 2. The figures signify thetime expressed in minutes which passes until the overpressure decreasesto zero.

                  Table 2                                                         ______________________________________                                        Incorporated phosphorus compounds of formula (I)                              Exple No.                minutes                                              ______________________________________                                        --                       119                                                  29                       179                                                  30                       193                                                  31                       200                                                  32      (Ba - salt)      229                                                  32      (Ni - salt)      207                                                  32      (Zn - salt)      290                                                  33                       195                                                  ______________________________________                                    

In a further series of tests 0.07% of4,4'-methylen-bis-(2,6-ditert.butylphenol) and 0.13% ofdilaurylthiodipropionate were used for the fundamental stabilization ofthe polypropylene and for the rest checked comparatively as describedabove. The results are summarized in the following table 3.

                  Table 3                                                         ______________________________________                                        Incorporated phosphorus compounds of formula (I)                              Exple. No.                  minutes                                           ______________________________________                                        --                          48                                                 3                          96                                                 5                          61                                                 6                          102                                                9                          78                                                10                          84                                                12                          105                                               13                          165                                               14                          81                                                15                          105                                               18                          102                                               19                          177                                               20                          98                                                21                          96                                                26                          89                                                27                          60                                                ______________________________________                                    

B. stabilization against brownish discoloration

While incorporating 0.2% of the stabilizer2,2'-methylen-bis-(4-methyl-6-tert.butylphenol) in polypropylene atabout 220° a brownish discoloration takes place. This discoloration maybe avoided if 0.1% of a compound of formula (I) is incorporated at thesame time.

In the ageing of small plates of polypropylene in a furnace at 140° astrong brownish discoloration takes place after only one day if theplastics only contains 0.2% of2,2'-methylen-bis-(4-methyl-6-tert.butylphenol). If the plasticsfurthermore contains 0.1% of a compound of the above table 1 it remainscolourless after 4 days at 140°. Formulae of representative benzenephosphonous acid compounds of the foregoing examples are as follows:

EXAMPLE 3 ##SPC10## EXAMPLE 16 ##SPC11## EXAMPLE 19 ##SPC12## EXAMPLE 26##SPC13## EXAMPLE 31

What is claimed is:
 1. A method of stabilizing material against theeffect of light, oxygen or heat which comprises incorporating in orapplying to the surface of an organic material which is sensitive tosaid effect an effective amount of a stabilizing agent of the formula##SPC14##wherein Y is oxygen or sulphur and n is 1 or 2,in free acid orsalt form.
 2. A process according to claim 1, wherein any salt form isan inorganic cation containing salt.
 3. A process according to claim 1wherein any salt form is a calcium, zinc, sodium, potassium, aluminium,barium or nickel salt.
 4. The method of claim 1 wherein n is
 1. 5. Themethod of claim 1, wherein Y is oxygen.
 6. The method of claim 1,wherein the stabilizing agent is of the formula ##SPC15##
 7. The methodof claim 1, wherein the susceptible material comprises a plasticsmaterial.
 8. The method of claim 7, wherein the plastics material isselected from cellulose acetate, cellulose propionate, celluloseacetobutyrate, polyethylene, polypropylene, polyvinyl chloride,polyvinyl chloride-acetate, polyamides, polystyrene, ethyl cellulose,cellulose nitrate, polyvinyl alcohol, silicon rubber,melamine-formaldehyde and urea-formaldehyde resins, allyl cast resins,polymethylmethacrylate, polyesters and polyacrylonitrile.
 9. The methodof claim 1, wherein between 0.01 and 5% of the stabiizing agent, basedon the weight of the susceptible material, is incorporated in or appliedto said material.